Hydroforming process using improved silica-alumina catalyst base



July 14, 1959 c. E. HEMMINGER HYDROFORMING PROCESS USING IMPRovED sILrcA-ALUMINA cATALYsT BASE 2 Sheet'sSheet 1 'A Filed D60. 21. 1954 ANo N14 00 1007. wmvxm Naw mbqvq :200ml @0.9i YuunJW ,Ommh

mbml, $22.23.?

July 14, 1959 c. E. HEMMINGER 2,894,900

, HYDROFORMING PROCESS USING IMPROVED SILICA-ALUMINA CATALYST BASE 2 Sheets-Sheet 2 Filed-Dec. 21. 1954 har'lesghflemmirzger 5 ave n Los United States Patent HYDRFORMING PROCESS USING IMPROVED SILICA-ALUMINA CATALYST BASE Charles E. Hemminger, Westfield, NJ., assignor to Esso Research and Engineering Company, a corporation of Delaware Application December 21, 1954, Serial No. 476,702 7 claims. (ci. 20s-13s) The present invention relates `to the preparation of new and improved aluminas which are especially useful as supports for active hydrotreating catalysts components. The present invention also relates to the process of hydro'treating hydrocarbons, and in particular it relates to hydrofonmingfnaphthas containing naphthenes in order to produce high anti-knock rating gasoline motor fuel constituents by contacting the feed naphthas at elevated temperatures and pressures with molybdenum oxide or other known hydroforming catalysts carried on a suitable support, such as alumina.

The invention relates more particularly to the hydrotreating of n'aphthas with catalysts containing alumina as the support or spacing agent, in which the alumina is present' in a state in which it is more efficient and otherwise more suitable than thelarg'e multiplicity of catalyst supports which have heretofore been proposed or used.

Hydroforming is customarily dened as an operation in which a hydrocarbon, such as a naphtha, is contacted at elevated temperatures and pressures in the presence of added hydrogen with a solid catalyst material. There is no net consumption of hydrogen during the process ordinarily. The process involves (l) dehydrogenation of naphthencs to form the corresponding aromatics, (2) aromatization of paraiiinic hydrocarbons, (3) isomerization of hydrocarbons wherein, for example, straight chain paratiins rearrange to form branch chain hydrocarbons and S-membered carbo-cyclic rings are converted to 6- membered carbo-cyclic rings, and (4) hydrocracking of parains. When properly operated, the process should yield a maximum amount of C4-ihydrocarbons and minimum amounts of dry gas and carbon.

The main object of the present invention is to provide an improved alumina support for active' hydrotreating' catalyst components.

It is a further object of this invention to provide a catalyst base for use in hydroforming which is adapted to promote the conversion of low octane hydrocarbon feed stock into gasoline constituents of high octane rating in good yields.

Another object of the present invention is to provide a hydroforming catalyst of high activity and long catalyst life.

A further object of the invention is to provide a catalyst base of improved efliciency.

Another object of the present invention is to provide a hydroforming catalyst which, when in the form of a powder, is adapted for use as a dense iluidized bed in a hydroforming zone, which powdered catalyst possesses high resistance to attrition.

Stated briey, the present invention provides a catalyst base or spacing agent for active hydrotreating catalyst components which is prepared by treating sodium aluminate in aqueous solution with aluminum sulfate and adding from l to 5 weight percent silica, preferably 2 weight percent (based on the A1203 content of the spacing agent), thereafter spray-drying the base and adding, as by impregnation, dry mix technique, etc., known hydro- "ice treating catalyst components such as compounds of metals of groups V-VIII of the periodic system as well as certain of the metals themselves such as molybdenum oxide, chromium oxide, cobalt oxide, vanadium oxide, tungsten oxide, molybdates and chromates, especially cobalt molybdate, suldes such as molybdenum sulfide, nickel-tungsten sulfide, platinum, palladium, rhodium, and the like.

In carrying out the present process of hydrofonming, a naphtha feed stock is vaporized and heated to ar temperature Within the range of from about 900-l050 F. These naphtha' vapors contain substantial amounts of naphthenic hydrocarbons, some aromatics and some parafns, and the feed stock is one which may be a virgin naphtha, a cracked naphtha, or a mixture of the two.

However, since one of the main features of the present invention resides in the manner in which the base or spacing agent for the active component of the hydroforming catalyst is made, complete details as to the best method for preparing this base will now be set forth.

ln the accompanying drawing there is set forth in Figure I, diagrammatically, a flow sheet indicating the steps for preparing the improved alumina base for the hydroforming catalyst, and in Figure ll, a ow plan depicting the essential apparatus of a hydroforming plant.

Referring in detail to the drawing, 1 represents a mixing tank provided with a suitable stirrer 2 to which the following are added:

From storage 3, which contains an aqueous solution of sodium aluminat'e in a concentration by weight of 20% A1203 with 8 weight percent excess NaOH, there is charged via line 4 to tank 1, a quantity of this sodium aluminate material. Simultaneously, from storage 5, there isv withdrawn through line 6 and charged to tank 1 a quantity of aluminum sulfate. From storage 7, which contains sodium silicate, this material isV Withdrawn through line 8 and also charged to tank 1.. Dilution water is also added to the tank 1 from lines 9 and 10, respectively.

The ingredients listed above are vigorously stirred by causing rotation of agitator 2. The proportions of they aluminum-containing ingredients mentioned above are such that two-thirds of the alumina precipitate comes from the sodium aluminate and one-third from the aluminum sulfate. Sufficient sulfuric acid to adjust the pH of the mixture in tank 1 to about 9-10, preferably about 9.5, is added to tank 1 through line 11. The mixture in tank 1 is maintained at a temperature of about 40-l20 F., 60-80 F. preferred, and pressure in the tank is atmospheric. Precipitation of the alumina is accomplished in a few minutes, say, 3-5 minutes. p

An aqueous slurry contai 'ng the precipitated alumina is withdrawn from tank 1 through line 12 and then pumped by pump 13 through line 14 to a lter feed tank 15. The concentration of A1203 by weight in thisl feed tank is about 1.2%. The slurry in tank 15 `is withdrawn through line 16 and thence pumped by pump 17 through line 18 to a primary filter 19, wherein the said slurry is filtered, and the tilter cake comprising the alumina is withdrawn at 20 and charged to a mixing tank 21 provided With driven agitat-ing means 22, and to which tank dilution water is added v-ia line 23. Referring again` to lter 19, the filtrate is discarded. The purpose of ltering the slurry is to separate the alumina from excess alkali and other impurities, which alumina is then delivered to tank 21 and mixed with fresh water .to facilitate subsequent spray drying.

rThe aqueous medium containing the alumina in tank 21 is Withdrawn through line 24 and then pumped by pump 25 throughl line 26 to a mixing tank 27 provided with driven agitator means 28, and to which a further quantity of water is added through line 29. After thorough stirring in 27 (as is accomplished in tank 21),

the material is withdrawn from tank 27 through line 30, thence passed through a pump 31, thence passed through line 32, through to a high pressure pump 33, which latter pump delivers the slurry via line 34 to a spray dryer 35 The succession of dilutions and the ltering step, previously described, serve to remove from association with the alumina substantially all of the extraneous material (e.g., sodium ions, sulfate ions, etc.) so that material delivered to spray dryer 35 contains approximately 5.6 parts percent by weight of total solids, of which parts by weight is A1203.

Spray dryer 35 may be of any conventional type, such as a Swenson or Bowen spray dryer type. The temperature conditions maintained in the spray dryer to effect the desired dehydration are substantially the following, namely, the inlet temperature is about 800 F. While the outlet temperature is about 300 F. The spray dried alumina is withdrawn through line 36 and delivered to tank 37 provided with a suitable driven agitating means 3S, and to which water is added through line 39. Again, the alumina is agitated in the aqueous medium and the resultant slurry is withdrawn through line 40, and pumped -by a pump 41, through line 42 into tank 43 provided with driven agitating means 44. The aqueous medium is vigorously agitated for several minutes and the slurry is withdrawn through line 45, passed through pump 46 and line 47 to a wash filtering means 48 where it is contacted with acidified wash water obtained from manifold 49 to `branch line 50. The washed precipitate is withdrawn from filter 48 through line 51 and charged to the dilution tank 52. provided with a driven stirring means 53 to which tank water is added through line 54. The alumina is again vigorously agitated in this aqueous medium for a few minutes, thence withdrawn through line 55 and pumped by pump 56, through line 57 to a second wash filter 58 on which latter filter it is again treated with the aqueous wash water contained in manifold 49 which is fed to said lter through line 59. The precipitate is withdrawn from the wash lter 58 through 60 and delivered to a dilution tank 61 provided with a driven stirrer 62 and to which dilution water is added through line 63. In this tank 61 the alumina-containing aqueous medium is vigorously stirred for a few minutes (again, say, 3-5 minutes), thence Withdrawn through line 64 and pumped by pump 65 through line 66 to a third Wash iilter 66 where, again, it is treated with aciditied water withdrawn from manifold 49 through line 67. The alumina is withdrawn from wash filter 66 via line 68 and passed through a steam tube dryer 69, and the dry product is finally recovered from line 70 and delivered toA storage. It will be understood that any suitable drying means may be employed in lieu of the steam tube dryer previously mentioned. It is also pointed out that the acidified Wash water in manifold 49 contains sulfuric acid equivalent to 14 ygrams calcium sulfate per gallon of liquid.

There is .thus indicated by the accompanying schematic flow plan the succession of steps performed in a preferred method of making an alumina composition also containing silica.

In order further to describe the invention, it is pointed out that in tank 1 dilute aluminum sulfate is mixed with partially acidifed sodium aluminate solution. The solution concentrations are adjusted to give a precipitate in tank 1 containing about 1.2 weight percent alumina. The quantity of aluminum sulfate added is carefully controlled so as to reach the desired pH of 9-l0.

The gel slurry is pumped to a filter tank and is dewatered on the primary lilter 19. It is pointed out that the rate of iiltering is quite sensitive to the pH of alumina precipitation. For example, at pH values in the range of -10.3 it is very diicult to dewater the slurry, and consequently the pH in the tank 1 must be maintained 4 below 10, and preferably within the range of from 9-9.5', whereupon the filter rate is :greatly increased.

The spray-dried .base prepared as explained above is in the form of microspheres and possesses a hard glassy appearance.

In preparing a hydroforming catalyst the vbase or carrier is impregnated with the water soluble molybdenum salt which is, at the same time, heat decomposable. The impregnated base is dried, heated and nally calcined. The amount of molybdenum salt impregnated into the base is such as to give a molybdenum oxide (M003) content of about 10% based on the total weight of the catalyst. As much as l5-20% molybdenum oxide may be added for special catalysts. It will be understood, of course, that other known hydrotreating, hydroforming and/or aromatizing catalysts such as chromium oxide, vanadium oxide, tungsten oxide, cobalt oxide,

, nickel oxide, molybdenum sulfide, cobalt molybdate,

nickel-tunsten sulfide, platinum, palladium, and the like, may -be incorporated into the lbase prepared as described above. Furthermore, the catalyst may be prepared by dry mixing the active component of the catalyst with the base and heating. The present invention does not go to the method of incorporating the active component of the catalyst into the base, and, therefore, any known procedure may be employed.

In Figure II there is shown the essentials of an apparatus in which a continuous hydroforming operation may be carried out employing a uidized catalyst technique. Referring in detail to Figure Il, represents a reactor containing a bed of powdered uidized catalyst extending from grid G to an upper dense phase level L. The hydrocarbon to be hydroforrned, say, a virgin naphtha containing 35 volume percent of naphthenes with a relatively small amount of aromatics and a major proportion of paraiin hydrocarbons, is charged to the system via line 101, thence passed through a furnace 102 where it is heated to a temperature of around 950- 1000" F., and thence passed via line 103 into a lower portion of a bed of catalyst C, but above the grid G1 in reactor 100. Simultaneously, a hydrogen-containing gas in line 104 (this gas is obtained from the product recovery system and commonly referred to as recycle gas) is heated in furnace 105 to a temperature of, say, 1200 F., and thence passed via line 106 into the bottom of reactor 100. This recycle gas usually contains 65-4 75% hydrogen, the remainder being normally gaseous hydrocarbons. The following conditions are maintained in reactor 100:

Supercial velocity of gasiform ma- 0.51.0 it. per sec.

terial in reactor 100.

Residence time of reactants in re- 30-120 seconds.

actor 100.

Under the conditions disclosed above, the desired reaction occurs and the product admixed with hydrogen passes from a dense phase extending from G to L into a light phase suspension of catalyst in gasiform material, extending from L to the top of the reactor. Before discharge from the reactor, the gasiform material is forced through a plurality of gas-solids separators S (one shown) wherein entrained catalyst is separated from the gasiform material and returned to the dente phase through dip pipes d (one shown). The raw product emerges from the reactor 100 through line 107 and thence is charged to the bottom portion of a scrubber 10S wherein it ows countercurrently upward against the downilowing oil charged to scrubber 108 through line 109. The downcoming oil, which is cooler than the gasi form material charged to the scrubber 108, washes out whatever catalyst is still entrained in the vapors and causes` condensation of the higher boiling polymers present in the crude product. The portion of the product which undergoes condensation, plus the added scrubbing oil, plus the catalyst removed from the gasiforin material, is withdrawn as a slurry from the bottom of scrubber 108: through line 110. This slurry may be returned to the. reactor 100 or rejected from the system. The uncondensed gasiform material is withdrawn from scrubber 108 overhead through'line 111 andA is charged toa product. recovery system 112 wherein the hydroformat is recovered and hydrogen gas is also recovered for recycle to line 104.

Since the catalyst undergoes contamination by carbonaceous and other deposits during the hydroforming operation in reactor'100, it is necessary to regenerate the catalyst. Towardv this end c-atalyst is withdrawn from the reactor 100 through drawol line 113 carrying the usuali gas taps t and controlled by a valve 114- and charged into a stream of air in line 115 wherein it is formed into a suspension and carried into regenerator 116 where it is formed into a fluidized bed C1 extending from a grid G1 to an upper dense phase level L1. In a manner entirely analogous to that in which the bed of uidized catalyst was formed in the reactor 100, the catalyst in regenerator 116 is formed into a second fluidized bed, mainly, by controlling the superficial velocity of the upflowingregeneration gas. Thetreatment of the fouled catalyst in regenerator 116, or other oxygencontaining gas, substantially frees the catalyst of contaminating carbonaceous and sulfurous deposits, and the regeneration fumes pass from the dense phase into an upper dilute phase extending from L1V to the top of the reactor. Before the fumes are rejected from the regenerator 116 they are forced through a series of gas-solids separating devices S1 (one shown) wherein entrained catalyst is separated from the said fumes and returnedv to the dense phase through a pluralityof dip pipes d1 (one` shown). In order to prevent overheating of the catalyst in regenerator 116, a cooling fluid in line 117 i5 Chargedl to a coil 11S disposed in the bed of catalyst whereinY heatis abstracted from the `said bed of catalyst, the cooling fluid being withdrawn through line 119. The regeneratedcatalyst is withdrawn from regenerator 116 through drawotf pipe 120 carrying the usual gas taps t and controlled by a valve 121 and charged into a stream of recycle gas, inline 122, wherein it is formed into a suspension and returned to the reactor. Y

The temperature in the regenerator is maintained between 11501200 F. and the circulation rate of cata-V lyst from the regenerator to the reactor is from 1 to 3 parts of catalyst per part of oil.

If desired, the catalyst may be treated with hydrogen in a separate vessel in the case where the catalyst contains a VI group metal oxide, such as molybdenum oxide, to partially reduce the said oxide to a lower valency state. Furthermore, water may be added to the catalyst entering the reactor. This water, however, is preferably added to the recycled hydrogen-containing gas so as to provide a concentration of water entering the reactor of some 1/2 to 1 mol percent H2O per mol of H2 entering the reactor.

In order further to explain the present invention,` the following data are set forth.

EXAMPLE I The catalyst used here was one in which the base consisted of about 97.1 weight percent A1203 and 2.9 weight percent SiOz. This base carried about M003 based on the total weight of the catalyst and carrier. The catalyst had the following physical characteristics:

(a) Surface area m.2/g 13 5 (b) Pore volume cc./g' .48

6 This. catalyst is utilized in hydrofornlng a feed of the following characteristics:

A naphtha feed of the above characteristics was hydroformed in the reaction zone maintained at a pressure of about 200 p.s.i.g. while maintaining a temperature in said reaction zone of 925 F. Hydrogen was charged to the reaction zone in the amount of about 5000 cubic feet measured to standard conditions per barrel of oil. The concentration of hydrogen in the hydrogen-containing `gas was about 65%.

Operating as above indicated to obtain a octane number (research) product, the following results were obtained as indicated in column A below. In column B the same feed stock was treated in exactly the same manner as the feed stock of column A, but in this case a conventional carrier or base was used to support the molybdenum oxide used in both runs.

It can be seen from the immediately foregoing table that the use of the new and improved base or carrier of the present invention has the following advantages:

(l) Improved liquid yield (less dry gas) (2) Lower carbon (3) Higher activity (4.), Improved volatility These advantages are apparent from a study of the table immediately above.

In the fluid operation it is essential that the powdered catalyst have good attrition resistance. In other words, the catalyst must have suicient mechanical strength to withstand physical disintegration when employed during a process utilizing the uidized catalyst technique. The data below show that the catalyst A which contains the. improved base had superior attrition resistance to the conventional catalyst B, as follows:

Attrtion resistance, lbs. of 0-40 micron material formed per day per lbs. of 40+ micron material reactor.y 0. 5 2. 0

Catalysts supported upon alumina prepared in accordance with the present invention, particularly those consisting of molybdenum oxide alone or admixed with cobalt oxide, molybdenum sulfide, nickel-tungsten sulfide, or cobalt molybdate, are useful in other hydrotrcating operations. Specifically, catalysts containing to 20 Weight percent cobalt molybdate are especially valuable for hydroiining of heating oil fractions boiling in the range of from 400-1100 F., particularly cracked oil fractions boiling within this range. The hydroiining operation conducted on the cracked -oil is desirably a mild hydrolining operation.

The temperatures used in the hydroining treatment are in the range from about 400 F. to 700 F., preferably in the range from about 500 F. to 650 F. Pressures employed are in the range from 50 to 250 pounds per square inch, preferably in the range from about 100 to 200 pounds per square inch. The feed rats are ordinarily in the range from about 1-16 volumes of liquid per volcertain stocks are conducted under conditions whereby the hydrogen consumption ranges from 150 to 600 standard cubic feet of hydrogen per barrel of oil. These operations used heretofore in the art secured a substantial sulfur reduction (50% to 90% In the so-callcd mild hydroiining operation operating conditions are adjusted so that the hydrogen consumption in standard cubic feet per barrel does not exceed 60 and is preferably less than 40. Furthermore, the extent of the sulfur reduction when utilizing the mild hydroning conditions is often as little as about The effectiveness of the catalysts of the present invention in the hydrolining of heating oils may be more clearly seen from the following experiments.

In evaluating these catalysts, experiments were conducted in which heating oils were hydrofined according to the principles Set forth. Heating oils used n these experiments had the inspections indicated in the following table:

Table l Stock A Stock B Stock C Stock D West Texas Doctor 700 F.E.P. Blend of Light Sweeteued Heavy Thermal and Vlrgin West Texas Catalytic Catalytic Heating Oil Virgin Heating Oil Heating Oil Heating Oil Gravity, API 21. 9 22. 9 Distillatlon:

IBP, F 402 385 5% at oF 490 476 10%. 508 494 20r 531 516 T 652 532 cr 671 548 Z7 593 566 U 610 682 633 600 050 618 670 638 9.30 690 653 FBP, "F 696 668 Recovery, percent 97.0 98.0 Carbon Residue (10% Bottoms), Wt. percent:

Unblended 14 13 Blended with Stock B 10 19 Blending Value. 15 33 Potential Sediment, Mg./ ml 3.6 0.5; 1. 4 Suspended Sediment, Mg/100 ml 0. 2 Color, TR 13% 13 Colorhold, TR 1% Doctor Test DNP NP Westphal Gravity 9202 9171 Bromne Number, cg./g 15. 6 8. 7 Mercaptan Number, mg. S/100 3. 3 4. 3 Total Sulfur, Wt. percent 1.118 1. 124

ume of catalyst per hour. Preferred feed rates are most often in the range from 1-5 v./v./h1'. The hydrogen in the gas to the hydroiining unit may vary from 50 to 100% This means that, for example, dilute hydrogen from a hydroformer can be used in the hydroining process. A particularly desirable method of hydroning is to recycle `appreciable quantities of hydrogen to the hydroiining unit in order to prevent carbonization `of the catalyst.

It is to be understood that the mild hydrofinng conditions are secured by the adjustment of the above-named operating conditions. yFor instance, if a relatively high liquid feed rate is used as compared to the amount of catalyst present, the higher temperature range may be employed. On the other hand, if a Very active catalyst is used, it is desirable to use a relatively high feed rate or to use a relatively low temperature. The mild hydrotining conditions are measured by the .amount of hydrogen consumption per barrel or oil feed. Conventional In these experiments a catalyst was employed which contained about 15% of cobalt molybdate supported on an alumina obtained by the reaction of sodiumaluminate, aluminum sulfate and sodium silicate in an aqueous medium maintained -at a pH of about 9 to 10. The alumina precipitated by this technique was filtered, washed and dried and impregnated with cobalt molybdate, all as specilically described in connection with Figure 1. For comparative purposes, the heating oils identilied Were also hydroned with a cobalt molybdate catalyst supported on a conventional form of silica-free alumina and also a commercially available form of cobalt mo- 70 lybdate supported on alumina.

In a tirst series of experiments, heating oil A, identitied in Table I, Was hydroned with the catalyst of this invention; the operating conditions and the results of this treatment are indicated in Table Il' for two typical hydroiining operations utilized for the desulfurization of 75 test runs:A

Table ll [HYDROIllII'IlGlv WEST TEXAS LIGHT VIRGIN HEATING OIL (STOCK A) OVERl CATALYST OF THE PRESENT INVENTION Run A Run B Operating Conditions:

Temperature, F 599 602 Feed Rate, v./hr./v 2.32 5. 20 Pressure, p.s.i.g. 204 201 Feed Gas:

Rate, s.c../b 630 369 Percent FT- 100 100 Product Inspections:

Distillation- IBP, F 320 310 390 390 402 400 418 416 431 428 443 492 455 453 467 v 465 480 478 493 491 Carbon Bottoms), Wt. Percent:

Unhlended 0.00 0.00 Blended with Stock D 0.03 0. 03 Blending Value -0. 07 0. 07 Sulfur, Wt. Percent 0.08 0.16 Doctor Test Pass Pass It will be noted from thisY data that the hydroining of heating o-il stock A incontact with the catalysts of the present invention serves to reduce the carbon residue of the treated heating oil to zero. The blended carbon residue values shown were obtained by blending the treated heating oil in a 50-50 proportion withl a caustic washed heating oil having a carbon residue on 10% bottoms of 0.10; this was stock D, identified in Table I. It will be observed that the linal blend had acarbon residue value of only 0.03. The blending value indicated in the table is obtained by calculating the carbon residue which would be expected on the basis of the averaged values of the blended stocks as compared to the value actually obtained. For example, since hydroiined stock A had a carbon residue of 0, While stock D had a carbon residue of 0.13, it could be expected that a 50-50 blend of these stocks would provide a carbon residue of about 0.07. Since the actual carbon residue of the blend was only 0.03, however, the blending value of hydroned stock A is calculated to be 0.07.

In other words,v this data shows that by employing the catalyst of this invention, the treated heating oil has the unexpected property of actually reducing the carbon residue inspection on blending with an inferior oil below the value which could be expected on the basis of average inspection values. This data demonstrates that heating oil hydroned in contact with the catalyst of this invention exhibits a synergistic compatibility on blending with heating oil which has not been specially processed.

In a second series of experiments to evaluate the catalysts of the present invention, heating oil C, identilied in Table I, was subjected to a mild hydrofining treatment. The conditions applied and results of this treatment are shown in Table III.

Table III HYDROFINING HEAVY CATALYTIC HEATING OIL (STOCK C) OVER CATALYST OF THE PRESENT IN- VENTION Operating conditions:

10 Production inspections:

Distillationf- IBP,. E. 395 5% 480 10%` 502 20%. 529 30%- 55.1 4.0%. 571 50% 591 60%. 610 70%, 628 647 Carbon residue (10% bottoms), wt. percent:

Unblended' 0.02 Blended with 50% of' Stock B 0.02 Blending value 0.01 Sulfur, wt. percent 0.46 Doctor test Pass It will be observed fromk this` data that the catalyst of this invention was extremely eiective in improving the burningt characteristics of the heatingV oil which was treated, reducing the carbon residue value of this oilto only 0.02. The blended carbon residue value indicated in` the table was obtained by blending the heating oil which was treated in 50-50 proportions with a doctor sweetened virgin heating oil B of the nature indicated in Table I. Again, it will be observed that the hydroning treatment with the catalyst of this invention resulted in a negative blending4 value, demonstrating an unexpected superiority of the catalyst for improving heating oils.

As brought out by the data of Tables II and III, the catalyst of this invention is remarkably effective in improving the burning quality of heating oils. The superiority of this catalyst is particularly marked by the characteristic that on blending heating oils, whichy have been hydroned in contact with catalysts produced in accordance with this invention, withl other normally incompatible heating oils, an unexpected improvement in the nal blended carbon residue values results. In View of these results, it may readily be seen that these catalysts can be used to substantially improve the total output of blended heating oil from a refinery by reducing the proportion of this heating oil which must be subjected to special processing to pass burning quality inspections.

For comparative purposes, reference may be made to comparable hydroining runs using conventional catalysts. ln one such experimental run, heating oil A, indicated in Table I, Was treated with a cobalt molybdate catalyst supported on a conventional silica-free aluminak base. The conduct of this process and the results obtained are set forth in Table IV.

Table IV HYDROFINING VIRGIN HEATING OIL (STOCK A) OVER CONVENTIONAL COBALT MOLYBDATE CATALYST Operating conditions:

l11 Table IV.-Con1nued 90% 508 95% 520 FBP, F 536 Recovery, percent 98.0 Loss, percent Carbon residue (10% bottoms), wt. percent:

Unblended .06 Blended with 50% of Cracked H.O. (0.18 carbon Residue) .11 Blending value .04 Color, Tr 211/2 Colorhold, TR 21 Doctor test Passes Westphal gravity .8367 Bromine number Mercaptan number, mg. S/ 100 ml. 0.39 Sulfur, weight percent .045

It will be noted from this data that while the conventional hydroiining catalyst was capable of improving the burning characteristics of the heating oil, this improvement was not nearly as marked as that obtained by the use of the catalyst of this invention. Again, it will be noted that the blending value of the treated heating oil was a positive rather than a negative value, indicating that the heating oil is somewhat less compatible for blending purposes than that produced with the catalyst of this invention.

Again, for comparative purposes, a heating oil hydroning run was conducted employing a commercially available form of cobalt molybdate on alumina. From previous experimental work, it has been established that this commercial catalyst was the most active commercially available catalyst. This catalyst was employed to hydrofine heating oil A, identiied in Table I. The conduct and results of this experiment are shown in Table V.

Table V HYDROFINING VIRGIN HEATING OIL (STOCK A) OVER COMMERCIALLY AVAILABLE HYDROFINING CATA- LYST Operating conditions:

Temperature, F 600 Feed rate, v./V./hr 1.02 Reactor pressure, p.s.i.g 200 Total gas feed (reactor inlet):

Percent hydrogen 100 Hydrogen rate, s.c.f./b 1066 Product inspections:

Gravity, API 37.3 Distillation- IBP, F 312 5% 386 400 415 30% 427 40% 442 50% 453 60% 466 70% 478 80% 491 90% 507 95% 520 FBP, F 536 Recovery, percent 98.3 Loss, percent Carbon residue (10% bottoms), wt. percent:

Unblended .02 Blended with 50% of cracked H.O. (carbon residue 0.18) .11 Blending value .04 Color, TR {-l9(S) Colorhold (RS. test), TR +16(S) Doctor test Passes l2 Westphal gravity .8361 Bromine number, cg./g Mercaptan number, mg.S/ ml 0.0 Total sulfur, wt. percent .017

Again, it will be observed that use of the conventional catalyst in this hydroning operation failed to completely eliminate blending incompatibility as indicated by the higher blending value.

To recapitulate briey, the present invention relates to preparing improved alumina catalyst supports and catalysts made therefrom. The hydrotreating catalysts forming the subject matter of the present invention consist of the alumina carrier prepared from the materials and by the techniques described and a conventional active hydrotreating catalystcomponent such as molybdenum oxide, chromium oxide, cobalt oxide, nickel oxide, tungsten oxide, vanadium oxide, cobalt molybdate, molybdenum sulfide, nickel-tungsten sulde, platinum, palladium, and the like.

The present invention relates to the use of catalyst supports of the type described containing 1 to 5 Weight percent of silica in the hydrotreating of hydrocarbon fractions. It has been found that the inclusion of silica in the catalyst carrier or base greatly improves the catalyst composition for the silica in the carrier yields a catalyst composition of good activity, good selectivity, and also profvides a catalyst which in the form of a powder of iluidizeable size possesses good resistance to attrition when employed in the form of a fluidized bed in a hydroforming or other hydrotreating process. The percentage of silica may be varied from 0.5 to 5.0% according to the service to which the catalyst is to be subjected or the desired results. The low silica content is used Where a minimum degree of hydrocracking of the paraiins is desired.

With respect to the proportions of sodium aluminate and aluminate sulfate used in preparing the present catalyst carrier or base, these may vary somewhat from the proportions heretofore given. It has been found, however, that both salts should be used for best results. Furthermore, during the several washings of the slurry or precipitate originally formed, the sodium content of the base material is reduced to not more than one-tenth of 1% sodium expressed as NaOH.

As pointed out previously, in preparing a molybdenum oxide-containing catalyst, a good procedure is the socalled dry-mix procedure in which molybdenum oxide (M003) is mixed with the proper amount of the present base and heated to a temperature of from l0001400 F., whereupon the molybdenum oxide is vaporized and distributed homogeneously throughout the base material. At the higher temperatures, the incorporation of the molybdenum oxide into the base is accomplished by this procedure in a matter of a few minutes.

In the case of a platinum-containing catalyst, the intermediate concentrate method is preferably employed, namely, the improved base is impregnated so as to contain, say, 5-l0% fby weight of platinum and then mechanically mixed with the present base in proportion such that the tinal mixture will contain from about 0.2-0.5 weight percent platinum based on the total weight of the catalyst.

The catalysts prepared according to the foregoing disclosure have been found to possess greatly improved properties when used in the form of a uidized bed since tests in a pilot plant unit and also in a commercial fluid hydroforming plant have demonstrated that the present new catalysts possess high activity, selectivity, and resistance to attrition. The method of spray drying the cata- `lyst is instrumental in enabling control of the particle size of the catalyst. The catalyst has also been found to be stable at the high temperatures utilized in regenerating the catalyst and the catalyst has also demonstrated that its activity is maintained for a long period of time.

This application is a continuation-impart of application Serial No. 318,000, led October 31, 1952, and now abandoned.

What is claimed is:

1. The process of hydroforming hydrocarbon fractions boiling Within naphtha boiling range which comprises: contacting feed naphtha vapors in admixture With a hydrogencontaining gas with a uidized bed of nely divided catalyst comprising a carrier containing a major proportion of alumina and a minor proportion of silica upon which a hydroforming catalyst is distributed in a hydroforming reaction zone, said carrier being prepared by reacting together sodium aluminate, aluminum sulfate, and sodium silicate in an aqueous medium maintained at a pH of from 9 to 10 followed by filtering of the resultant precipitate, 'washing and drying the precipitate, maintaining the reactants and catalyst in said reaction zone under active hydroforming conditions of temperature, pressure, and residence time and recovering from said reaction zone a hydroformed naphtha product of improved octane rating.

2. The method set forth in claim 1 in which the catalyst carrier contains from about 0.5 to 5.0 Weight percent of silica.

3. The method set forth in claim l in which the precipitate is spray dried.

4. The method set forth in claim 3 in which the catalyst carrier is in the form of hard microspheres.

5. The method of preparing hydroforrning catalysts which possess high activity and high attrition resistance when used in processes involving the use of the fluidized solids technique Which comprises reacting together sodium aluminate, aluminum sulfate, and sodium silicate in an aqueous medium maintained at a pH of about 9 to 10, filtering and Washing the resultant precipitate, drying, and heating the resultant silica-containing alumina, and incorporating an active hydroforming catalyst into the aluminasilica composition.

6. The method as set forth in claim 5 in which the alumina-silica composition is spray dried to form hard, attrition-resistant microspheres and thereafter mixed while the silica alumina carrier and the hydroforming component are in the dry state, and heating at a temperature suiiciently high to vaporize the hydroforming component comprising molybdenum oxide and cause it to be uniformly distributed throughout the alumina-silica composition.

7. The method as set forth in claim 5 in which the alumina-silica composition is impregnated with an aqueous solution of a compound of a platinum group metal, thereafter dried and heated to activate the thus formed catalyst composition.

References Cited in the le of this patent UNITED STATES PATENTS 2,429,981 Bates Nov. 4, 1947 2,437,532 Huffman Mar. 9, 1948 2,446,799 Winding Aug. 10, 1948 2,463,508 Bates Mar. 8, 1949 2,487,563 Layng Nov. 8, 1949 2,508,014 Davidson May 16, 1950 2,602,772 Haensel July 8, 1952 

1. THE PROCESS OF HYDROFORMING HYDROCARBON FRACTIONS BOILING WITHIN NAPHTHA BOILING RANGE WHICH COMPRISES CONTACTING FEED NAPHTHA VAPORS IN ADMIXTURE WITH A HYDROGENCONTAINING GAS WITH A FLUIDIZED BED OF FINELY DIVIDED CATALYST COMPRISING A CARRIER CONTAINING A MAJOR PROPORTION OF ALUMINA AND A MINOR PROPORTION OF SILICA UPON WHICH A HYDROFORMING CATALYST ID DISTRIBUTED IN A HYDROFORMING REACTION ZONE, SAID CARRIER BEING PREPARED BY REACTING TOGETHER SODIUM ALUMINATE, ALUMINUM SULFATE, AND SODIUM SILICATE IN AN AQUEOUS MEDIUM MAINTAINED AT A PH OF FRROM 9 TO 10 FOLLOWED BY FILTERING OF THE RESULTANT PRECIPITATE, WASHING AND DRYING THE PRECIPITATE, MAINTAINING THE REACTANTS AND CATALYST IN SAID REACTION ZONE UNDER ACTIVE HYDROFORMING CONDITIONS OF TEMPERATURE, PRESSURE, AND RESIDENCE TIME AND RECOVERING FROM SAID REACTION ZONE A HYDROFORMED NAPHTHA PRODUCT OF IMPROVED OCTANE RATING. 